Abstract
Transition metal phosphides have been extensively studied for catalytic applications in water splitting. Herein, we report an in situ phosphorization of zeolitic imidazole frameworks (ZIF-67) to generate amorphous cobalt phosphide/ZIF-67 heterojunction on a self-supporting copper foam (CF) substrate with excellent performance for hydrogen evolution reaction (HER). The needle-leaf like copper hydroxide was anchored on CF surface, which acted as implantation to grow ZIF-67. The intermediate product was phosphorized to obtain final electro-catalyst (CoP/Cu2O@CF) with uniform particle size, exhibiting a rhombic dodecahedron structure with wrinkles on the surface. The electrochemical measurement proved that CoP/Cu2O@CF catalyst exhibited excellent HER activity and long-term stability in 1.0 mol·L−1 KOH solution. The overpotential was only 62 mV with the Tafel slope of 83 mV·dec−1 at a current density of 10 mA·cm−2, with a large electrochemical active surface area. It also showed competitive performance at large current which indicated the potential application to industrial water electrolysis to produce hydrogen. First-principle calculations illustrated that benefit from the construction of CoP/ZIF-67 heterojunction, the d-band center of CoP downshifted after bonding with ZIF-67 and the Gibbs free energy (ΔGH*) changed from −0.18 to −0.11 eV, confirming both decrease in overpotential and excellent HER activity. This work illustrates the efficient HER activity of CoP/Cu2O@CF catalyst, which will act as a potential candidate for precious metal electrocatalysts.
References
Zhang X. The development trend of and suggestions for hydrogen energy industry. Engineering, 2021, 7(6): 719–721
Wang J, Gao Y, Kong H, Kim J, Choi S, Ciucci F, Hao Y, Yang S, Shao Z, Lim J. Non-precious-metal catalysts for alkaline water electrolysis: operando characterizations, theoretical calculations, and recent advances. Chemical Society Reviews, 2020, 49(24): 9154–9196
Cheng N, Stambula S, Wang D, Banis M N, Liu J, Riese A, Xiao B, Li R, Sham T K, Liu L M, Botton G A, Sun X. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction. Nature Communications, 2016, 7(1): 13638
Shi Y, Zhang B. Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction. Chemical Society Reviews, 2016, 45(6): 1529–1541
Liang H, Liu J. Insights on the corrosion and degradation of MXenes as electrocatalysts for hydrogen evolution reaction. ChemCatChem, 2022, 14(6): e202101375
Theerthagiri J, Murthy A P, Lee S J, Karuppasamy K, Arumugam S R, Yu Y, Hanafiah M M, Kim H S, Mittal V, Choi M Y. Recent progress on synthetic strategies and applications of transition metal phosphides in energy storage and conversion. Ceramics International, 2021, 47(4): 4404–4425
Jiang Y, Lu Y, Lin J, Wang X, Shen Z. Water splitting: a hierarchical MoP nanoflake array supported on Ni foam: a bifunctional electrocatalyst for overall water splitting. Small Methods, 2018, 2(5): 1800028
Wang R, Dong X Y, Du J, Zhao J Y, Zang S Q. MOF-derived bifunctional Cu3P nanoparticles coated by a N,P-codoped carbon shell for hydrogen evolution and oxygen reduction. Advanced Materials, 2018, 30(6): 1703711
Liu T, Liu D, Qu F, Wang D, Zhang L, Ge R, Hao S, Ma Y, Du G, Asiri A M, Chen L, Sun X. Enhanced electrocatalysis for energy-efficient hydrogen production over CoP catalyst with nonelectroactive Zn as a promoter. Advanced Energy Materials, 2017, 7(15): 1700020
Guan C, Xiao W, Wu H, Liu X, Zang W, Zhang H, Ding J, Feng Y P, Pennycook S J, Wang J. Hollow Mo-doped CoP nanoarrays for efficient overall water splitting. Nano Energy, 2018, 48: 73–80
Guan C, Wu H, Ren W, Yang C, Liu X, Ouyang X, Song Z, Zhang Y, Pennycook S J, Cheng C, Wang J. Metal-organic framework-derived integrated nanoarrays for overall water splitting. Journal of Materials Chemistry A, 2018, 6(19): 9009–9018
Suo N, Han X, Chen C, He X, Dou Z, Lin Z, Cui L, Xiang J. Engineering vanadium phosphide by iron doping as bifunctional electrocatalyst for overall water splitting. Electrochimica Acta, 2020, 333: 135531
Wang S, McGuirk C M, d’Aquino A, Mason J A, Mirkin C A. Metal-organic framework nanoparticles. Advanced Materials, 2018, 30(37): 1800202
He T, Kong X J, Li J R. Chemically stable metal–organic frameworks: rational construction and application expansion. Accounts of Chemical Research, 2021, 54(15): 3083–3094
Jadhav H S, Bandal H A, Ramakrishna S, Kim H. Critical review, recent updates on zeolitic imidazolate framework-67 (ZIF-67) and its derivatives for electrochemical water splitting. Advanced Materials, 2022, 34(11): e2107072
Kharissova O V, Kharisov B I, Ulyand I E, García T H. Catalysis using metal-organic framework-derived nanocarbons: recent trends. Journal of Materials Research, 2020, 35(16): 2190–2207
Zhai Y, Ren X, Yan J, Liu S. High density and unit activity integrated in amorphous catalysts for electrochemical water splitting. Small Structures, 2020, 2(4): 2000096
Guo C, Shi Y, Lu S, Yu Y, Zhang B. Amorphous nanomaterials in electrocatalytic water splitting. Chinese Journal of Catalysis, 2021, 42(8): 1287–1296
Anantharaj S, Noda S. Amorphous catalysts and electrochemical water splitting: an untold story of harmony. Small, 2020, 16(2): e1905779
Yang M, Jiang Y, Qu M, Qin Y, Wang Y, Shen W, He R, Su W, Li M. Strong electronic couple engineering of transition metal phosphides-oxides heterostructures as multifunctional electrocatalyst for hydrogen production. Applied Catalysis B: Environmental, 2020, 269: 118803
Wang Z, Xiao B, Lin Z, Xu Y, Lin Y, Meng F, Zhang Q, Gu L, Fang B, Guo S, Zhong W. PtSe2/Pt heterointerface with reduced coordination for boosted hydrogen evolution reaction. Angewandte Chemie International Edition, 2021, 60(43): 23388–23393
Yu Z, Li Y, Martin-Diaconescu V, Simonelli L, Ruiz Esquius J, Amorim I, Araujo A, Meng L, Faria J L, Liu L. Highly efficient and stable saline water electrolysis enabled by self-supported nickel-iron phosphosulfide nanotubes with heterointerfaces and under-coordinated metal active sites. Advanced Functional Materials, 2022, 32(38): 2206138
Zhang L, Zheng Y, Wang J, Geng Y, Zhang B, He J, Xue J, Frauenheim T, Li M. Ni/Mo bimetallic-oxide-derived heterointerface-rich sulfide nanosheets with Co-doping for efficient alkaline hydrogen evolution by boosting volmer reaction. Small, 2021, 17(10): e2006730
Inta H R, Ghosh S, Mondal A, Tudu G, Koppisetti H V S R M, Mahalingam V. Ni0.85Se/MoSe2 interfacial structure: an efficient electrocatalyst for alkaline hydrogen evolution reaction. ACS Applied Energy Materials, 2021, 4(3): 2828–2837
Wang T, Tao L, Zhu X, Chen C, Chen W, Du S, Zhou Y, Zhou B, Wang D, Xie C, Long P, Li W, Wang Y, Chen R, Zou Y, Fu X Z, Li Y, Duan X, Wang S. Combined anodic and cathodic hydrogen production from aldehyde oxidation and hydrogen evolution reaction. Nature Catalysis, 2021, 5(1): 66–73
Guo X, Xing T, Lou Y, Chen J. Controlling ZIF-67 crystals formation through various cobalt sources in aqueous solution. Journal of Solid State Chemistry, 2016, 235: 107–112
Qazi U Y, Javaid R, Tahir N, Jamil A, Afzal A. Design of advanced self-supported electrode by surface modification of copper foam with transition metals for efficient hydrogen evolution reaction. International Journal of Hydrogen Energy, 2020, 45(58): 33396–33406
Jiang Y, Liang J, Yue L, Luo Y, Liu Q, Kong Q, Kong X, Asiri A M, Zhou K, Sun X. Reduced graphene oxide supported ZIF-67 derived CoP enables high-performance potassium ion storage. Journal of Colloid and Interface Science, 2021, 604: 319–326
Liu H, Guan J, Yang S, Yu Y, Shao R, Zhang Z, Dou M, Wang F, Xu Q. Metal–organic-framework-derived Co2P nanoparticle/multi-doped porous carbon as a trifunctional electrocatalyst. Advanced Materials, 2020, 32(36): e2003649
Zhang X, Zheng R, Jin M, Shi R, Ai Z, Amini A, Lian Q, Cheng C, Song S. NiCoSx@cobalt carbonate hydroxide obtained by surface sulfurization for efficient and stable hydrogen evolution at large current densities. ACS Applied Materials & Interfaces, 2021, 13(30): 35647–35656
Yang H, Chen Z, Guo P, Fei B, Wu R. B-doping-induced amorphization of LDH for large-current-density hydrogen evolution reaction. Applied Catalysis B: Environmental, 2020, 261: 118240
Shan X, Liu J, Mu H, Xiao Y, Mei B, Liu W, Lin G, Jiang Z, Wen L, Jiang L. An engineered superhydrophilic/superaerophobic electrocatalyst composed of the supported CoMoSx chalcogel for overall water splitting. Angewandte Chemie International Edition, 2020, 59(4): 1659–1665
Beltrán-Suito R, Menezes P W, Driess M. Amorphous outperforms crystalline nanomaterials: surface modifications of molecularly derived CoP electro(pre)catalysts for efficient water-splitting. Journal of Materials Chemistry A, 2019, 7(26): 15749–15756
Anjum M A R, Okyay M S, Kim M, Lee M H, Park N, Lee J S. Bifunctional sulfur-doped cobalt phosphide electrocatalyst outperforms all-noble-metal electrocatalysts in alkaline electrolyzer for overall water splitting. Nano Energy, 2018, 53: 286–295
Zhao Y, Jin B, Zheng Y, Jin H, Jiao Y, Qiao S Z. Charge state manipulation of cobalt selenide catalyst for overall seawater electrolysis. Advanced Energy Materials, 2018, 8(29): 1801926
Li J, Xu Y, Liang L, Ge R, Yang J, Liu B, Feng J, Li Y, Zhang J, Zhu M, Li S, Li W. Metal–organic frameworks-derived nitrogen-doped carbon with anchored dual-phased phosphides as efficient electrocatalyst for overall water splitting. Sustainable Materials and Technologies, 2022, 32: e00421
Song M, Zhang Z, Li Q, Jin W, Wu Z, Fu G, Liu X. Ni-foam supported Co(OH)F and Co-P nanoarrays for energy-efficient hydrogen production via urea electrolysis. Journal of Materials Chemistry A, 2019, 7(8): 3697–3703
Wei C, Sun S, Mandler D, Wang X, Qiao S Z, Xu Z J. Approaches for measuring the surface areas of metal oxide electrocatalysts for determining their intrinsic electrocatalytic activity. Chemical Society Reviews, 2019, 48(9): 2518–2534
McCrory C C, Jung S, Peters J C, Jaramillo T F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. Journal of the American Chemical Society, 2013, 135(45): 16977–16987
Kitchin J R, Norskov J K, Barteau M A, Chen J G. Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals. Journal of Chemical Physics, 2004, 120(21): 10240–10246
Medford A J, Vojvodic A, Hummelshøj J S, Voss J, Abild-Pedersen F, Studt F, Bligaard T, Nilsson A, Nørskov J K. From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis. Journal of Catalysis, 2015, 328: 36–42
Jiao S, Fu X, Huang H. Descriptors for the evaluation of electrocatalytic reactions: d-band theory and beyond. Advanced Functional Materials, 2021, 32(4): 2107651
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant No. 41573103) and the Shandong Natural Science Foundation (Grant Nos. ZR2021MB049, ZR2022QB211) of China.
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In situ growth of phosphorized ZIF-67-derived amorphous CoP/Cu2O@CF electrocatalyst for efficient hydrogen evolution reaction
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Qi, R., Liu, X., Bu, H. et al. In situ growth of phosphorized ZIF-67-derived amorphous CoP/Cu2O@CF electrocatalyst for efficient hydrogen evolution reaction. Front. Chem. Sci. Eng. 17, 1430–1439 (2023). https://doi.org/10.1007/s11705-023-2320-1
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DOI: https://doi.org/10.1007/s11705-023-2320-1